KR20160027161A - Polycyclic compounds - Google Patents

Abstract

The present invention relates to a compound having a polycyclic structural unit and an electronic device, particularly an organic electroluminescent device, containing the compound.

Description

Polycyclic compounds {POLYCYCLIC COMPOUNDS}

The present invention relates to compounds suitable for use in electronic devices. The present invention also relates to a method of manufacturing the same and an electronic device.

BACKGROUND OF THE INVENTION Electronic devices containing organic, organometallic and / or polymeric semiconductors are becoming increasingly important and are used in many commercial products due to cost reasons and their performance. Examples are organic photoreceptors (e.g., triarylamine-based hole transport materials) in photocopiers, organic or polymeric light emitting diodes (OLEDs or PLEDs) . Organic solar cells (O-SC), organic field-effect transistors (O-FET), organic thin film transistors (O-TFT), organic integrated circuits (O-IC), organic optical amplifiers and organic laser diodes (O- Is an advanced stage of development and can be very important in the future.

Most such electronic devices have the following general substrate structure that can be adjusted for a particular application, regardless of their respective end use:

(1)

(2) Electrodes, often metallic or inorganic, but also composed of organic or polymeric conductive materials,

(3) charge injection layer (s) or interlayer (s) to compensate for non-planarity in electrodes ("planarization layer") often comprised of a conductive doping polymer,

(4) organic semiconductors,

(5) possibly further charge transport, charge injection or charge blocking layer,

(6) the counter electrode, the substance specified in (2)

(7) Encapsulation.

The arrangement is a general structure of an organic electronic device, which can combine the various layers, and in the simplest case the result is an arrangement consisting of two electrodes with an organic layer therebetween. In this case, the organic layer fulfills all functions including the emission of light in the case of OLEDs. This type of system, for example based on poly (p-phenylene), is described in WO 90/13148.

Known electronic devices have useful property profiles. However, there is a continuing need to improve the properties of such devices.

This characteristic particularly includes the lifetime of the electronic device. An additional specific problem is the energy efficiency of the electronic device to achieve the stated purpose. In the case of organic light emitting diodes, which may be based on low molecular weight compounds or polymeric materials, the light yield must be high enough so that a minimum amount of power, in particular, must be applied to achieve a luminous flux. In addition, the minimum voltage must also need to achieve the defined brightness.

It is therefore an object of the present invention to provide novel compounds which yield electronic devices with improved properties. A particular objective is to provide a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron blocking material, an electron blocking material, or the like, which exhibits improved characteristics in terms of efficiency, operating voltage, lifetime, chromaticity coordinate and / or color purity, And / or radiator material. In addition, the compounds must be processable in a simple manner and exhibit particularly good solubility and film formation.

Additional objects of providing electronic devices with excellent performance at a constant quality and at very low cost can be considered.

In addition, electronic devices must be able to be used or adapted for many purposes. More particularly, the performance of electronic devices must be maintained over a wide temperature range.

Surprisingly, this and other matters which may be inferred or recognized from the associations discussed herein by the introductory section, which are not expressly stated, are achieved by the compounds having all the features of claim 1. Suitable modifications to the compounds of the present invention are protected in the dependent claims cited in claim 1.

Accordingly, the present invention provides compounds comprising at least one of the structures of formula (I) and / or (II)

Wherein the symbols used are as follows:

X is in each case the same or different and is CR or N;

E is a divalent bridge wherein the E group is taken together with the carbon atom to which it is attached to form a 5- or 6-membered ring;

Y is O, S, C (R) 2, C (R) = C (R), N (R), B (R), Si (R) 2, C = O, C = NR, C = C ( (R) ₂ , S = O, SO ₂ , C (R) ₂ -C (R) ₂ , P (R) and P (= O) R;

R is the same or different at each occurrence and, H, D, F, Cl , Br, I, N (R 1) 2, CN, NO 2, OH, COOH, C (= O) N (R 1) 2, _{^{Si (R 1) 3, B}} (OR 1) 2, C (= O) R 1, P (= O) (R 1) 2, S (= O) R 1, S (= O) 2 R 1, OSO ₂ R ¹ , a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms each of which can be optionally substituted with one or more radicals R ^1, where one or more non-adjacent CH ₂ groups ^{R 1 C = CR 1, C≡C} , Si (R 1) 2, C = O, NR 1, O, S or CONR ¹ and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN), or have 5 to 60 aromatic ring atoms and in each case one or more R ¹ An aromatic or heteroaromatic ring system which may be substituted by a radical, or an aromatic or heteroaromatic ring system containing 5 to 40 aromatic ring atoms It has at least one R ¹ radical in the aryloxy group or a heteroaryl group which may be substituted by oxy group, or a 5 to 40 aromatic ring atoms to have at least one R ¹ radical aralkyl or heteroaralkyl optionally substituted by a group, or 10 to 40 which has an aromatic ring atom may be substituted by one or more radicals R ¹ diarylamino group, a di-heteroaryl-amino group, or an aryl-amino-heteroaryl group; Two adjacent R radicals may together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;

R ¹ is the same or different at each occurrence, is H, D, F, Cl, Br, I, N (R 2) 2, CN, NO 2, Si (R 2) 3, B (OR 2) 2, C (= O) R ² , P (═O) (R ² ) ₂ , S (═O) R ² , S (═O) ₂ R ² , OSO ₂ R ² , straight chain alkyl of 1 to 20 carbon atoms, A thioalkoxy group, an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which may be substituted by one or more R ² radicals, wherein one or more non-adjacent CH ₂ groups are ^{R 2 C = CR 2, C≡C} , Si (R 2) 2, C = O, NR 2, O, may be replaced by S or CONR ^2, one or more hydrogen atoms, where May be replaced by D, F, Cl, Br, I, CN or NO ₂ ), or an aromatic or heteroaromatic ring having 5 to 60 aromatic ring atoms and in each case optionally substituted by one or more R ² radicals Or one having 5 to 40 aromatic ring atoms and one On the R ² radical aryloxy or heteroaryl which may be substituted by an oxy group, or a 5 to 40 aromatic ring atoms to have aralkyl or heteroaralkyl optionally substituted with one or more R ² radical group, or a 10 to A diarylamino group, a diheteroarylamino group or an arylheteroarylamino group having 40 aromatic ring atoms and being substituted by at least one R ² radical; At the same time, two or more adjacent R < ¹ > radicals together or together with R < ¹ > may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;

R ² is in each case the same or different and is H, D, F or an aliphatic, aromatic and / or heteroaromatic hydrocarbyl radical of 1 to 20 carbon atoms in which the hydrogen atom may also be replaced by F; At the same time, two or more R < ² > substituents may together form a mono- or polycyclic aliphatic ring system.

In this context, "adjacent carbon atoms" or adjacent "CH ₂ groups" means that the carbon atoms are bonded directly to one another.

The term that two or more radicals can form a ring together will be understood to mean in the context of the present application, in particular that the two radicals are bonded to one another by chemical bonding. This is illustrated by the following diagram:

.

.

It will also be understood that the above mentioned mention also means that when one of the two radicals is hydrogen, the second radical is bonded at the position at which the hydrogen atom is bonded to form a ring. This will be illustrated by the following scheme:

.

.

In the context of the present invention an aryl group contains from 6 to 40 carbon atoms; Heteroaryl groups contain from 2 to 40 carbon atoms and at least one heteroatom in the context of the present invention, with the proviso that the total sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. The aryl or heteroaryl group may be substituted by a single aromatic cycle such as benzene or a simple heteroaromatic cycle such as pyridine, pyrimidine, thiophene or the like, or a fused aryl or heteroaryl group such as naphthalene, anthracene, phenanthrene, Quinoline, isoquinoline, and the like.

In the context of the present invention, the aromatic ring system contains 6 to 60 carbon atoms in the ring system. In the context of the present invention, a heteroaromatic ring system contains from 1 to 60 carbon atoms and at least one heteroatom in the ring system, with the proviso that the total sum of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. The aromatic or heteroaromatic ring system need not only contain only an aryl or heteroaryl group in the context of the present invention but also two or more aryl or heteroaryl groups may be substituted with a nonaromatic unit (preferably an atom other than H) For example, a carbon, nitrogen or oxygen atom or a system intervening by a carbonyl group. For example, the system such as 9,9'-spirobifluorene, 9,9'-diarylfluorene, triarylamine, diaryl ether, stilbene and the like is also considered to be an aromatic ring system in the context of the present invention, It is considered that two or more aryl groups are involved, for example, by a linear or cyclic alkyl group or a silyl group. In addition, a system in which two or more aryl or heteroaryl groups are directly bonded to each other, for example, biphenyl or terphenyl, will also be regarded as an aromatic or heteroaromatic ring system.

Cycloalkyl, alkoxy or thioalkoxy groups are understood to mean monocyclic, bicyclic or polycyclic groups in the context of the present invention.

In the context of the present invention, a C ₁ - to C ₄₀ -alkyl group, wherein the individual hydrogen atoms or CH ₂ groups may also be replaced by the abovementioned groups, is for example methyl, ethyl, n-propyl, i-propyl, Propyl, n-butyl, i-butyl, s-butyl, t-butyl, Heptyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, Cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1 -bicyclo [2.2.2] octyl, 2-bicyclo [2.2.2] octyl, 2- -Dimethyl) octyl, 3- (3,7-dimethyl) octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, N-hept-1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl- -Dimethyl-n-dodec-l-yl, Dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-di Ethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1- 1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1- Yl, 1- (n-propyl) cyclohex-1-yl, 1- n-hexyl) cyclohex-1-yl, 1- (n-octyl) cyclohex-1-yl- and 1- (n-decyl) cyclohex-1-yl radical. The alkenyl group means, for example, an alkenyl group such as ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl . An alkynyl group is understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. The C ₁ - to C ₄₀ -alkoxy group may for example be methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, Butoxy or 2-methylbutoxy.

An aromatic or heteroaromatic ring system which has 5-60 aromatic ring atoms and which in each case can be substituted by the above-mentioned radicals and which can be bonded to an aromatic or heteroaromatic system through any desired position is, for example, There can be mentioned benzene, naphthalene, anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzofluoranthene, naphthacene, pentacene, Cis- or trans-monobenzoindenobifluorene, cis- or trans-monobenzoindenobifluorene, cis- or trans-monobenzoindenobifluorene, cis- or trans-monobenzoindenobifluorene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropylene, Or a combination of two or more of dicarboxylic acids such as trans-dibenzoindenofluorene, tolylsenes, isotoluxes, spirobutylenes, spiroisocitloxenes, furans, benzofurans, isobenzofurans, dibenzofurans, thiophenes, benzothiophenes, Pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, Quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthymidazole, pyridimidazole, Pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthoxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, Diazafilene, 2,3-diazaphylenes, 1,6-diazaphylenes, 1, 6-diazaphylenes, 1, , 8-diazafylene, 4,5-diazapyrane, 4,5,9,10-tetraazaferylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorovin, naphthyridine, azacarbazole, Benzocarboline, phenanthroline, 1,2,3-tri , 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4- Oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5- Triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2, Is understood to mean a group derived from 3,5-tetrazine, purines, pteridines, indolizines and benzothiadiazoles.

E is the formula X = XX = X, XWX, WX = X, X = XW ( wherein, W is O, S, C (R) 2, N (R), B (R), Si (R) 2, Is selected from the group consisting of C = O, S = O, SO ₂ , P (R) and P (= O) R and X and R are in each case the same or different and as defined above. (I) and / or (II). Preferably, W is selected from O, S and N (R). More preferably, E forms an aromatic or heteroaromatic ring having 5 or 6 atoms with the carbon atoms to which it is attached.

The compounds also include one or more of the following structures of formula (Ia) and / or (IIa): < EMI ID =

Wherein the symbols used have the definitions given above.

Particularly preferred are compounds comprising at least one structure of the formulas (Ia1), (Ia2), (IIa1) and / or (IIa2)

Wherein the symbols used have the definitions given above.

Also preferred are compounds having at least one of the structures of the following formulas (Ia3) and / or (Ia4):

Wherein the symbols used have the definitions given above.

According to a further arrangement of the present invention, preferred compounds include one or more of the following structures of formula (Ib) and / or (IIb):

Wherein the symbols used have the definitions given above.

According to a further embodiment of the invention, highly preferred compounds comprise one or more of the following structures of formula (Ib-1) and / or (IIb-1)

Wherein the symbols used have the definitions given above.

Further preferred compounds include those of formula (Ic)

Wherein the symbols used have the definitions given above and E may in each case be the same or different.

It may also be the case that the compound has two or more bicyclic groups formed by structural elements comprising a group Y, wherein Y is in each case the same or different and is as defined above.

Preferably, the compound may have the structure of the formula CyE- (CyF) _n where the symbols and indices are as follows:

n is 2 or 3,

CyE is a structural element selected from the following formulas:

CyF is one or more structural elements selected from the following formulas:

In the formula, the symbols E, R, Y and X used has the definitions given, U is O, S, C (R) 2, N (R), B (R), Si (R) 2, C = O, S = O, sO 2, P (R) , and P (= O) is selected from R, where U is preferably O, N (R) and C (R) _2, very preferably O, and C (R) ₂ , particularly preferably C (R) ₂ , the dashed line in the formulas CyF-1 and CyF-2 represents a bond to CyE and the CyF group in each case is bonded to CyE at the position indicated by # .

In a further preferred embodiment of the invention, U is O.

This may particularly preferably be the case where CyF is one or more structural elements selected from the following formulas:

Wherein the symbols R, Y and X used have the definitions given in claim 1, the dashed lines of the formulas CyF-3 and CyF-4 represent a bond to CyE, and CyF represents the position indicated by # in each case To CyE].

Preferably no more than three X symbols in CyE and / or CyF are N, more preferably no more than two X symbols in CyC are N, and more preferably no more than one X symbol in CyC is N to be. Particularly preferably, all X symbols are CR.

A preferred embodiment of CyE group has the formula (CyE-28) to (CyE-52) (U in the formula is O, S, C (R) 2, N (R), B (R), Si (R) 2 , C = O, S = O , SO 2, P (R) , and P (= O) is selected from R, where U is preferably C (R) _2, and the position CyE group represented by # in each case Lt; RTI ID = 0.0 > CyF < / RTI >

.

.

This may also be the case when the compound has the structure of the formula CyG (CyH) _n , where CyG and CyH together form a ring in each case and the symbols and indices are as follows:

n is 2 or 3,

CyG is a structural element selected from the following formulas:

CyH is one or more structural elements selected from the following formulas:

[Wherein the symbols R, Y and X used has the definitions given, U is O, S, C (R) 2, N (R), B (R), Si (R) 2, C = O , S = O, SO is selected from _2, P (R), and P (= O) R, where U is preferably C (R) _2, and in the formula CyH-1 and CyH-2 the dashed line for the CyG And CyH is bonded to CyG at the position represented by o in each case to form a ring].

Preferably no more than three X symbols in CyG and / or CyH are N, more preferably no more than two X symbols in CyC are N, and more preferably no more than one X symbol in CyC is N to be. Particularly preferably, all X symbols are CR.

Particularly preferred CyG groups are those of the formulas (CyG-16) to (CyG-28)

[Wherein the symbols X has the above given definition, U is O, S, C (R) 2, N (R), B (R), Si (R) 2, C = O, S = O , SO ₂ , P (R) and P (= O) R, U is preferably C (R) ₂ and CyH is linked to CyG at each position represented by o to form a ring ].

(R < 1 >), R < 1 >, R < ¹ >, R & ^{_{2, CN, Si (R 1}} ) 3, B (oR 1) 2, C (= O) R 1, min C 1 -C 10 straight chain alkyl group or a C2 to 10 alkenyl group, or having 3 to 10 carbon atoms in the branched Or cyclic alkyl groups each of which may be substituted by one or more R < ¹ > radicals, wherein one or more hydrogen atoms may be replaced by D or F, or having 5 to 30 aromatic ring atoms and in each case one An aromatic or heteroaromatic ring system which may be substituted by at least one of the R < ¹ > radicals; At the same time, two adjacent R radicals together or together with R < ^{1 >} may also form a mono- or polycyclic, aliphatic or aromatic ring system. More preferably, these R radicals are the same or different in each case and are preferably H, D, F, N (R ¹ ) ₂ , a straight chain alkyl group of 1 to 6 carbon atoms or a branched or poetic group of 3 to 10 carbon atoms (Where one or more hydrogen atoms may be replaced by D or F), or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms and in each case optionally substituted by one or more R < ¹ > ≪ / RTI > At the same time, two adjacent R radicals together or together with R < ^{1 >} may also form a mono- or polycyclic, aliphatic or aromatic ring system.

The compounds of the invention comprising the structure of formula (I) and / or (II) may also be chiral, depending on the structure. This is especially the case when they contain a substituent, for example an alkyl, alkoxy, dialkylamino or aralkyl group, having one or more stereogenic centers. The base structure of the complex may also be a chiral structure, so that the formation of multiple pairs of diastereoisomers and enantiomers is possible. In such cases, the compounds of the present invention encompass both the different diastereomers or the corresponding racemates and mixtures of the individually isolated diastereoisomers or enantiomers.

Preferably, the compound may be in the form of an enantiomeric mixture, more preferably a diastereomeric mixture. As a result, the characteristics of electronic devices that can be obtained using the compounds of the present invention can be improved unpredictably. This characteristic particularly includes the lifetime of the device.

According to a preferred embodiment, compounds of the formula:

.

.

This may also be the case when the structure of formula (I) and / or (II) has a maximum content of bromine atoms of preferably 18% by weight, more preferably 10% by weight, particularly preferably 5% by weight. According to a preferred aspect of the present invention, the compounds of the present invention preferably have a maximum content of bromine atoms of 18% by weight, more preferably 10% by weight, particularly preferably 5% by weight.

(IIa), (IIa), (Ia1), (IIa1), (Ia2), (IIa2), (Ia3), (Ia4), (Ib) and structural formula and CyE- (CyF) _n and CyG (CyH) in the structure of the _n, the symbol X is the ratio of CR to N is preferably 2 or more, preferably 3 or more, more preferably 4 of (Ic) Or more.

Particularly preferred compounds include structures according to the following formulas:

Also particularly preferred compounds include structures according to the following formulas 60-67:

Compounds having at least one of the structures of formulas 60, 61, 64 to 67 are preferably present in the form of a diastereomeric mixture and / or may be used in its form.

Particularly preferred are those compounds having the structure of the following formulas (68) to (77):

Compounds having more than one structure of formulas 68 to 77 are preferably present in the form of a diastereomeric mixture or may be used in its form.

Also particularly preferred compounds include structures according to the following formulas 78-85:

The above-mentioned preferred embodiments can be combined with each other as desired. In a particularly preferred embodiment of the invention, the above-mentioned preferred embodiments are applied simultaneously.

The compounds of the present invention may theoretically be prepared by a variety of processes. However, the processes described below have been found to be particularly suitable.

Accordingly, the present invention also provides a process for preparing a compound comprising the structure of formula (I) and / or (II) by reacting at least one aldehyde with at least one aromatic or heteroaromatic amine and at least one bicyclic olefin . The reaction may also be carried out using a mixture of aldehydes, aromatic amines and / or bicyclic olefins. However, the reaction of the pure components is preferred in order to obtain the defined product.

An illustrative example of the reaction is shown by the following diagram:

The compounds of the present invention are preferably used in the Povarov reaction with an activated olefin to produce Lewis acid-catalyzed reaction of arylamine and aldehyde to yield imines and tetrahydroisoquinoline and its subsequent dehydrogenation ≪ / RTI > The order of the reaction of the imine formation and the povarob reaction can preferably be carried out as a one-pot process. The activated olefins used are, for example, bi- and tricyclic olefins of the bicyclo [2.2.1] (norbornene) and bicyclo [2.2.2] (verilen) types.

The Lewis acid used may be selected from the group consisting of basic element compounds such as boron halides, aluminum halides, gallium halides and indium halides and their adducts, more preferably boron trifluoride, boron trifluoride etherate, aluminum trichloride, gallium trichloride, indium tri Such as halides, halides, bismuth halides and antimony halides such as bismuth trichloride or other transition metals and lanthanide compounds, preferably Zr, Cu, Ag, Au, Zn, Y, La, Yb salts such as halides, .

The dehydrogenation of substituted tetrahydroisoquinolines can be carried out by known methods from the literature, for example, by transition metal-catalyzed dehydrogenation or transfer dehydrogenation, or by metal oxides (e.g., manganese dioxide) or quinones For example, DDQ).

Also, aldehydes having one and preferably two or more aldehyde group (s) can be used, and it is preferred to use aromatic or heteroaromatic aldehydes. Preferred aldehydes include the compounds described in the synthesis examples.

Preferred monoaldehydes include, for example, benzaldehyde (CAS 100-52-7), benzaldehyde substituted by an alkyl group, 2-naphthalaldehyde (CAS 66-99-9), 6-tert- (CAS 104461-06-5), 3-phenylbenzaldehyde (CAS 1204-60-0), 2-benzofurancarboxaldehyde (CAS 12046-69-9), 2-tert- butylpyrimidine-5-carbaldehyde CAS 4265-16-1), 3-dibenzofurancarboxaldehyde (CAS 51818-91-8), 9,9'-spiro [9H-fluorene] -2-carboxaldehyde (CAS 124575-66- 2) and [1,1 ': 3', 1 "-terphenyl] -5'-carboxaldehyde (CAS 220955-80-6).

Preferred dialdehydes are 1,3-phthalaldehyde (CAS 626-19-7), 1,4-phthalaldehyde (CAS 623-27-8), 1,5-naphthalenedicarboxaldehyde (CAS 7141-15-3 ), 1,6-pyrandicarboxaldehyde (CAS 252338-01-5) and 9,9'-spiro [9H-fluorene] -2,7-dicarboxaldehyde (CAS 856014-12-5) .

Also, aromatic and heteroaromatic amines having one and preferably two or more amine group (s) can be used. Preferred aromatic or heteroaromatic amines include the compounds described in the synthesis examples.

Preferred monoamines are, for example, anilines (CAS 62-63-3), 4-methylaniline (CAS 106-49-0), 3,5- dimethylaniline, 4-t-butylaniline (CAS 769-92-6 (CAS 92-67-1), 2-tert-butyl-5-aminopyrimidine (CAS 59950-55-9), 2-benzofuranamine (CAS 139266-08-3), 2 Aminobenzo [b] thiophene (CAS 4521-30-6), 1-aminonaphthalene (CAS 134-32-7), 8-aminoquinoline (CAS 578-66-5), 1-anthracene amine -49-1), 2-anthracene amine (CAS 613-13-8) and 1-phenanamine (9CI) (CAS 2876-22-4).

Preferred diamines include p-phenylenediamine (CAS 106-50-3), m-phenylenediamine (CAS 108-45-2), o-phenylenediamine (CAS 95-54-5), 1,5-naphthalene Diamine (CAS 2243-62-1) and 1,5-naphthyridine-4,8-diamine (CAS 64761-26-8).

Bicyclic olefins having 1, 2 or more double bond (s) can also be used. Preferred bicyclic olefins include the compounds described in the synthesis examples.

Preferred bicyclic olefins are norbornene (CAS 498-66-8), norbornadiene (CAS 121-46-0), 7,7-dimethyl norbornene (CAS 6541-60-2), benzonur (CAS 4453-90-1), 7-oxanorbornene (CAS 6705-50-6), 7-oxabenzonorbornadiene (CAS 573-57-9), bicyclo [2.2.2 ] -2-octene (CAS 931-64-6), bicyclo [2.2.2] octa-2,5-diene (CAS 500-23-2), bicyclo [2.2.2] octa- 7-triene (CAS 500-24-3) and 1,4-dihydro-1,4-ethenonaphthalene (CAS 7322-47-6).

It may be preferred to use Lewis acid as catalyst in the reaction, and advantageously boron trifluoride etherate (CAS 60-29-7) may be used.

In order to obtain a compound having the structure of the present invention, oxidation is generally carried out. For this purpose, standard oxidants, such as manganese dioxide or quinone, are suitable.

The above-described reaction is known to the person skilled in the art as theoretically called " Povarov reaction ", and is further described in the literature, for example in [J. Org. Chem. 75 (2010) 702-715 and Tetrahedron 65 (2009) 2721-2750.

Intermediates obtained after the reaction of one or more aldehydes with one or more aromatic amines and one or more bicyclic olefins can be converted in the coupling reaction.

Suitable reactions for C-C bonds and / or C-N bonds are well known to those skilled in the art and are described in the literature. Particularly suitable and preferred coupling reactions which cause all CC bonding are BUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASHIRA, And Hiyama (HIYAMA).

By such a process, the compounds of the present invention comprising a structure of formula (I) and / or formula (II) can be treated with a high purity, preferably 99%, if necessary followed by subsequent purification, for example recrystallization or sublimation. (As measured by < ¹ > H NMR and / or HPLC).

The compounds of the present invention may also be substituted by suitable substituents such as, for example, relatively long alkyl groups (about 4 to 20 carbon atoms), especially branched alkyl groups, or optionally substituted aryl groups such as xylyl, mesityl or branched Phenyl or quaterphenyl group, which results in solubility in standard organic solvents, such as toluene or xylene, that are soluble at room temperature with sufficient concentration to be able to process complexes from solution. Such soluble compounds are particularly suitable for processing from solution, for example in printing processes. It should also be emphasized that the compounds of the present invention comprising at least one structure of formula (I) and / or (II) already have improved solubility in such solvents.

The compounds of the present invention may also be mixed with a polymer. These compounds may also be incorporated covalently into the polymer. This is especially possible with compounds which are substituted by reactive leaving groups such as bromine, iodine, chlorine, boronic acid or boronic acid esters or by reactive polymerizable groups such as olefins or oxetanes. Which can be used as monomers for the preparation of corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably carried out via a halogen or boronic acid functional group or through a polymerizable group. Polymers can also be crosslinked through these types of groups. The compounds and polymers of the present invention can be used in the form of crosslinked or uncrosslinked layers.

Accordingly, the present invention also provides oligomers, polymers or dendrimers containing one or more of the above-mentioned structures of formula (I) and / or (II) or one or more compounds of the invention, wherein the compounds of formula (I) / RTI > and / or at least one bond to a polymer, oligomer or dendrimer of the structure of (II). According to the structure or linkage of the compounds of the formulas (I) and / or (II), they form side chains of the oligomer or polymer or are bonded in the main chain. The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The oligomer or polymer may be linear, branched or dendritic. In the case of repeating units of the compounds of the invention in oligomers, dendrimers and polymers, the same preferences apply as described above.

For the preparation of oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with further monomers. A copolymer in which the unit of the formula (1) or the above-mentioned preferred embodiment is present in an amount of 0.01 to 99.9 mol%, preferably 5 to 90 mol%, more preferably 20 to 80 mol%, is preferable. Suitable and preferred comonomers for forming the polymer backbone are fluorenes (for example according to EP 842208 or WO 2000/022026), spirobifluorene (for example according to EP 707020, EP 894107 or WO 2006/061181) , Paraphenylene (for example according to WO 92/18552), carbazole (for example according to WO 2004/070772 or WO 2004/113468), thiophene (for example according to EP 1028136), dihydrophenan (For example according to WO 2005/014689), cis- and trans-indenofluorene (for example according to WO 2004/041901 or WO 2004/113412), ketones (for example according to WO 2005/040302 ), Phenanthrene (for example according to WO 2005/104264 or WO 2007/017066) or a number of such units. Polymers, oligomers and dendrimers may contain further units such as, for example, hole transporting units, especially triarylamine based ones and / or electron transporting units.

In addition, the compounds of the present invention may have a relatively low molecular weight. The present invention thus also provides compounds wherein the molecular weight is preferably less than or equal to 10 000 g / mol, more preferably less than or equal to 5000 g / mol, particularly preferably less than or equal to 3000 g / mol.

Further, it is a characteristic of the compound that it is desirable that this is sublimable. Such compounds generally have a molar mass of less than about 1200 g / mol.

Also of particular interest are compounds of the present invention characterized by a high glass transition temperature. (I) and (II) having a glass transition temperature of at least 70 DEG C, more preferably at least 110 DEG C, even more preferably at least 125 DEG C and particularly preferably at least 150 DEG C, measured in accordance with DIN 51005 ≪ / RTI > are particularly preferred.

The compounds of the present invention may comprise one or more metal atoms selected from iridium, ruthenium, palladium, platinum, osmium or rhenium, preferably iridium or platinum. Such compounds are particularly suitable as phosphorescent emitters. For example, the above-described compounds 1 to 27 and the compounds A1 to A27 described in the examples can produce metal complexes that are reacted with platinum and / or iridium to be radiated.

In particular, metal complexes of the following formula (M-1) are preferred:

M (L) _n (L ') _m ????? (M-1)

Wherein the symbols and indices used are as follows:

M is iridium or platinum;

L is in each case the same or different and is a ligand comprising at least one of the structures of formula (I) and / or (II);

L 'is in each case the same or different and is any covalent ligand;

n is 1, 2 or 3;

m is 0, 1, 2, 3 or 4;

For example, the corresponding free ligand L, and optionally L ', is a metal alkoxide of formula (M-2), a metal ketoketonate of formula (M-3), a metal halide of formula (M- -5) or a metal complex of the formula (M-6): < EMI ID =

Wherein Hal is F, Cl, Br or I and L "is an alcohol, especially an alcohol or nitrile of 1 to 4 carbon atoms, especially acetonitrile or benzo Nitrile, and (anion) is a non-coordinating anion, such as a triplet.

It is also possible to use metal compounds, in particular iridium compounds (including both alkoxide and / or halide and / or hydroxyl and ketone ketone radicals). These compounds can also be charged. Corresponding iridium compounds particularly suitable as reactants are disclosed in WO 2004/085449. Especially suitable are _{[IrCl 2 (acac) 2]} -, for example, _{Na [IrCl 2 (acac) 2} ], as a ligand, metal complexes of acetylacetonate derivatives, such as Ir (acac) ₃ tris (2, 2,6,6-tetramethylheptane-3,5-dionate) iridium, and IrCl ₃ .xH ₂ O (wherein x is typically a number of 2 to 4).

Suitable platinum reactants are, for example, PtCl ₂ , K ₂ [PtCl ₄ ], PtCl ₂ (DMSO) ₂ , Pt (Me) ₂ (DMSO) ₂ or PtCl ₂ (benzonitrile) ₂ .

The synthesis of the complexes is preferably carried out as described in WO 2002/060910, WO 2004/085449 and WO 2007/065523. The heteroleptic complexes can be synthesized, for example, according to WO 2005/042548 as well. In this case, the synthesis may be activated, for example, also by thermal or photochemical methods and / or by microwave radiation. In a preferred embodiment of the invention, the reaction is carried out without the use of further solvents as a melt. "Melt" means that the ligand is in a molten form and the metal precursor is dissolved or suspended in such melt. For the activation of the reaction, which additionally may also be added to the salt containing a Lewis acid, for example, or AlCl _3.

The present invention further provides formulations comprising a compound of the invention or an oligomer, polymer or dendrimer of the invention and one or more further compounds. Additional compounds may be used, e. The additional compound may alternatively be an additional organic or inorganic compound also used in an electronic device, for example a matrix material. These additional compounds may also be polymeric.

The present invention furthermore relates to the use of the compound of the present invention and a compound selected from the group consisting of a fluorescent radiator, a phosphorescent emitter, a host material, a matrix material, an electron transport material, an electron injecting material, a hole conductor material, a hole injecting material, Lt; RTI ID = 0.0 > functionalized < / RTI > material.

The above-described compounds comprising the structures of formulas (I) and / or (II) or the preferred embodiments described above can preferably be used as active components in electronic devices. An electronic device is understood to mean an anode, a cathode and any device comprising one or more layers, which layer comprises one or more organic or organometallic compounds. Accordingly, the electronic device of the present invention comprises at least one layer containing an anode, a cathode and at least one compound comprising a structure of formula (I) and / or (II). A preferred electronic device is an organic electroluminescent device (OLED, PLED), an organic integrated circuit (O-IC), an organic electroluminescent device (OLED) containing one or more compounds comprising a structure of formula (I) and / (O-FET), an organic thin film transistor (O-TFT), an organic light emitting transistor (O-LET), an organic photovoltaic cell (O-SC), an organic photodetector, an organic photoreceptor, (O-FQD), a luminescent electrochemical cell (LEC), and an organic laser diode (O-laser). An organic electroluminescent device is particularly preferable. The active component is generally an organic or inorganic substance introduced between the anode and the cathode, for example, a charge injection, charge transport or charge blocking material, in particular a radiating and matrix material. The compounds of the present invention exhibit particularly good properties as spinning materials in organic electroluminescent devices. A preferred embodiment of the present invention is thus an organic electroluminescent device. In addition, the compounds of the present invention can be used for the production of singlet oxygen or for photocatalytic action.

The organic electroluminescent device includes a cathode, an anode, and at least one radiation layer. Apart from such a layer, it may also comprise additional layers such as, in each case, one or more of a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, an electron injection layer, an excitation blocking layer, / RTI > and / or organic or inorganic p / n junctions. At the same time, it is possible that one or more hole transporting layers are p-doped, for example, by metal oxides such as MoO ₃ or WO ₃ or (per) fluorinated electron-deficient aromatic systems and / or one or more electron transporting layers are n-doped . It is also possible that an interlayer is introduced between the two emissive layers, for example having exciton-blocking function and controlling the charge balance in the electroluminescent device. It should be noted, however, that not all of these layers need be present.

In this case, the organic electroluminescent device may contain a spinning layer, or it may contain a plurality of spinning layers. If there are a plurality of radiation layers, this preferably has several radiation maximums of 380 nm to 750 nm as a whole, and the overall result is white radiation; In other words, a variety of radioactive compounds capable of emitting fluorescence or phosphorescence are used in the radiation layer. Particularly preferred is a three-layer system in which three layers exhibit blue, green and orange or red emission (see, for example, WO 2005/011013 for a basic structure) or a system with three or more emission layers. The system may also be a hybrid system in which one or more layers fluoresces and one or more other layers emit phosphorescence.

In a preferred embodiment of the present invention, the organic electroluminescent device comprises a compound of the present invention comprising a structure of the formula (I) and / or (II) or the preferred embodiment described above, preferably an additional matrix material and / In combination with at least one radiation layer as a radioactive compound and / or a matrix material.

In such a case, the metal complex of the present invention comprising the structure of at least one compound of the present invention, preferably the structure of the formula (I) and / or (II) is preferably a compound having the structure of the formula (I) or (II) ≪ / RTI > may be used as the radioactive compound in the spinning layer. In addition, a matrix material lacking the structures of the formulas (I) and / or (II) may be combined with the metal complex of the present invention containing the structure of the formula (I) and / or the formula (II). It is also possible to use as the matrix material the compounds of the invention comprising the structure of formula (I) and / or (II), wherein such matrix material lacks the structure of formula (I) and / or (II) ≪ / RTI >

When the compound of the present invention comprising the structure of formula (I) and / or (II) is used as a radioactive compound in the spinning layer, it is preferably used in combination with one or more matrix materials. The mixture of compounds of the present invention and the matrix material comprising the structure of formulas (I) and / or (II) may comprise from 0.1 vol% to 99 vol%, preferably from 1 vol% (I) and / or (II), preferably from 5% to 90% by volume, more preferably from 3% to 40% by volume and especially from 5% to 15% by volume. Thus, the mixture is preferably 99.9 to 1 vol.%, Preferably 99 to 10 vol.%, More preferably 97 to 60 vol.%, Especially 95 to 85 vol.%, Based on the total radiator and mixture of matrix materials. To 85% by volume of the matrix material.

The matrix material used may be any material generally known for purposes of the prior art. The triplet level of the matrix material is preferably higher than the triplet level of the emitter.

Suitable matrix materials for the compounds of the present invention include, but are not limited to, ketones, phosphine oxides, sulfoxides and sulfones (e.g. according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680), triarylamines, Carbazole derivatives such as CBP (N, N-biscarbazolylbiphenyl), m-CBP or carbazole derivatives (WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527, 086851 or US 2009/0134784), indolocarbazole derivatives (for example according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (for example WO 2010/136109 or WO 2011 / (For example according to WO 2007/137725), silanes (for example, according to EP-A-0,172,905), azacarbazoles (for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160), bipolar matrix materials WO 2005/111172), azaborol or boronic esters (for example according to WO 2006/117052), diazacillol derivatives (for example, For example according to WO 2010/054729), diazappor derivatives (for example according to WO 2010/054730), triazine derivatives (for example according to WO 2010/015306, WO 2007/063754 or WO 2008/056746) Zinc complexes (for example according to EP 652273 or WO 2009/062578), dibenzofuran derivatives (for example according to WO 2009/148015), or crosslinked carbazole derivatives (for example, US 2009/0136779, WO 2010 / 050778, WO 2011/042107 or WO 2011/088877).

In addition, the compounds of the present invention can be used as a matrix material. In this case, the matrix material of the present invention can be used together with a radioactive compound containing at least one structure of the formula (I) and / or (II) or a radioactive compound which does not have the structure of the formula (I) and / or (II) have. In this context, it should be emphasized that the above-mentioned ratios of the matrix material to the radioactive compound correspond correspondingly.

It may also be desirable to use a number of different matrix materials, especially one or more electron-conductive matrix materials and one or more hole-conductive matrix materials, as a mixture. A preferred combination is, for example, the use of aromatic ketones, triazine derivatives or phosphine oxide derivatives and triarylamine derivatives or carbazole derivatives as a mixed matrix for the metal complexes of the present invention. It is also preferred to use a mixture of charge-transport matrix materials and electrically inert matrix materials that are not significantly involved, if any, in charge transport, for example as described in WO 2010/108579.

It is also preferred to use a mixture of matrices with two or more triplet radiators. In this case, a triplet radiator with a shorter wavelength emission spectrum serves as a cavity-matrix for a triplet emitter with a longer wavelength emission spectrum. For example, a compound of the present invention comprising the structure of formula (I) and / or (II) as a co-matrix for a longer wavelength radioactive triplet emitter, for example a green- or red- Can be used.

The compounds of the present invention may also be used as other functions in electronic devices, for example as hole transport materials in hole injection or transport layers, as charge generating materials or as electron blocking materials. The complex of the present invention can also be used as a matrix material for other phosphorescent metal complexes in the spinning layer.

The present invention also provides an electronic device, preferably an organic electroluminescent device, one or more compounds of the present invention and / or one or more oligomers, polymers or dendrimers of the present invention as electron-conducting compounds in one or more electron-conducting layers.

The present invention also relates to an electronic device, preferably an organic electroluminescent device, at least one hole-conducting layer, more preferably at least one compound of the invention as hole-conducting compound and / or at least one oligomer, polymer or dendrimer Lt; / RTI >

Preferred cathodes include metals having a low work function, metal alloys or various metals such as alkali-earth metals, alkali metals, metals or lanthanides (e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline-earth metals and silver, such as magnesium and silver. In the case of a multilayer structure, it is also possible to use an additional metal, for example Ag, which has a relatively high work function in addition to the mentioned metal, in this case for example Mg / Ag, Ca / Ag or Ba / Ag Combinations of the same metals are commonly used. It may also be desirable to introduce a thin intermediate layer of material having a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials useful for this purpose include alkali metal fluorides or alkali-earth metal fluorides as well as corresponding oxides or carbonates (e.g. LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO _3, etc.). Also useful for this purpose are organic alkali metal complexes such as Liq (lithium quinolate). The layer thickness of such a layer is preferably 0.5 to 5 nm.

A preferred anode is a material having a high work function. The anode preferably has a work function of greater than 4.5 eV against vacuum. First, metals with high redox potentials, such as Ag, Pt or Au, are suitable for this purpose. On the other hand, metal / metal oxide electrodes (e.g. Al / Ni / NiO _x , Al / PtO _x ) may also be preferred. For some applications, one or more of the electrodes must be transparent or partially transparent to enable irradiation of organic materials (O-SC) or radiation of light (OLED / PLED, O-laser). The preferred anode material is a conductive mixed metal oxide. Particularly preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). In addition, conductive doped organic materials, particularly conductive doped polymers, PEDOT, PANI or derivatives of such polymers, are preferred. It is also preferred if the p-doped hole transport material is applied to the anode as a hole injection layer, where suitable p-dopants are metal oxides such as MoO ₃ or WO ₃ or (per) fluorinated electron- Aromatic system. Suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or compound NPD9 (from Novaled). The layer simplifies the hole injection into a material having a low HOMO (i.e., a large HOMO with respect to magnitude).

In the additional layer, any material conventionally used in accordance with the prior art can be used, and those skilled in the art will be able to combine the materials of the present invention with any such material in electronic devices without having to practice the technique of the present invention .

The device is correspondingly structured, provides contact, and is finally sealed (depending on the application), since the lifetime of the device is shortened in the presence of water and / or air.

Also preferred is an electronic device, particularly an organic electroluminescent device, characterized in that one or more layers are coated by a sublimation process. In this case, the material is applied by deposition in a vacuum sublimation apparatus under an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. It is also possible that the initial pressure is even lower or even higher (for example, less than 10 ^-7 mbar).

Also preferred is an electronic device, particularly an organic electroluminescent device, characterized in that at least one layer is coated by OVPD (organic vapor phase deposition) process or with the aid of carrier gas sublimation. In this case the material is applied at a pressure of 10 ^-5 mbar to 1 bar. A particular case of this method is the OVJP (organic vapor jet printing) method in which the material is directly applied and structured by a nozzle (see, for example, MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

It is also contemplated that one or more of the layers may be formed by any suitable printing process, such as by spin coating, or by any printing method, such as screen printing, flexographic printing, offset printing or nozzle printing, An organic electroluminescent device characterized by being manufactured from a solution by thermal imaging, thermal imaging, thermal transfer printing or ink-jet printing. For this purpose, a soluble compound is required, which is obtained, for example, by a suitable substitution.

Electronic devices, particularly organic electroluminescent devices, can also be fabricated as a hybrid system by applying one or more layers from a solution and applying one or more other layers by deposition. For example, a radioactive layer comprising a compound of the present invention and a matrix material comprising a structure of formula (I) and / or (II) is applied from a solution and a hole blocking layer and / It is possible to apply a transport layer.

This method can be applied without difficulty to an electronic device, particularly an organic electroluminescent device, comprising the compound of the present invention having the structure of the formula (I) and / or (II) or the above-described preferred embodiment.

The electronic device of the present invention, particularly the organic electroluminescent device, is notable for one or more of the following remarkable advantages over the prior art:

1. An electronic device, particularly an organic electroluminescent device, comprising a compound, an oligomer, a polymer or a dendrimer having a structure of the formula (I) and / or the formula (II) as a radioactive substance, an electron-conducting substance or a hole- Has a lifetime.

2. An electronic device, particularly an organic electroluminescent device, comprising a compound, an oligomer, a polymer or a dendrimer having a structure of formula (I) and / or (II) as a radioactive substance, an electron-conducting substance or a hole- . More particularly, the efficiency is much higher than similar compounds that do not contain structural units of formula (I) or (II).

3. Compounds of the present invention, preferably comprising one or more metal atoms selected from Ir and Pt, in some cases have a very narrow emission spectrum, which yields high color purity, especially in the emission desired for display applications.

4. Compounds of the present invention, preferably comprising one or more metal atoms selected from Ir and Pt, have reduced aggregation compared to similar compounds which do not contain structural units of formula (I) or (II). This is evident at lower sublimation temperatures and higher solubilities, and in reduced triplet-triplet quenching in electroluminescent devices.

5. Compounds, oligomers, polymers and dendrimers of the invention having the structure of formula (I) and / or (II) exhibit very high stability and yield compounds with very long lifetimes.

6. The use of compounds, oligomers, polymers or dendrimers having the structures of the formulas (I) and / or (II) can avoid the formation of optical loss channels in electronic devices, especially organic electroluminescent devices. As a result, these devices feature high PL efficiency and thus high EL efficiency of the emitter, and excellent energy transfer of the matrix to the dopant.

7. The use of compounds, oligomers, polymers or dendrimers having the structure of formula (I) and / or (II) in the layer of an electronic device, particularly an organic electroluminescent device, yields high mobility of the electron conductor structure.

8. Compounds, oligomers, polymers and dendrimers having the structure of formula (I) and / or (II) are characterized by excellent thermal stability, and compounds with a molar mass of less than about 1200 g / mol have good sublimation properties .

9. Compounds, oligomers, polymers and dendrimers having the structure of formula (I) and / or (II) have excellent glass film formation.

10. Compounds, oligomers, polymers and dendrimers having the structure of formula (I) and / or (II) form very good films from solution.

These above-mentioned advantages are not accompanied by deterioration of the further electronic properties.

The present invention relates to a process for the preparation of a hole injecting material, a hole transporting material (HTM), a hole blocking material (HBM), an electron transporting material (ETM), an electron injecting material, an electron blocking material and / ) Or a blue mono-emitter (SEB), and / or the oligomers, polymers or dendrimers of the present invention in electronic devices.

It should be noted that variations of the embodiments described in the present invention are within the scope of the present invention. Any feature disclosed in the present invention may be interchanged for the same purpose or for alternative features that perform the same or similar purposes, unless this is clearly contravened. Accordingly, any feature disclosed in the present invention should be considered as an example from the inclusive series or as an equivalent or similar feature, unless otherwise indicated.

All features of the invention may be combined with one another in any manner so long as the particular features and / or steps are not mutually exclusive. This is particularly true of the preferred features of the present invention. Equally, features of non-essential combinations can be used separately (and not in combination).

Also, it should be noted that most features, and particularly the features of the preferred embodiments of the present invention, are inventive in nature and should not be regarded merely as part of the embodiments of the invention. In the case of this feature, independent protection may be required as a further or alternative to any currently claimed invention.

The technical teachings disclosed with the present invention can be extracted and combined with other examples.

The invention is described in detail by the following examples without any intention of restricting it thereto.

Those skilled in the art will be able to fabricate additional electronic devices of the present invention using the given details without having to practice the techniques of the present invention and thus to practice the invention beyond the full scope claimed.

Example

The following synthesis is carried out under a protective gas atmosphere in a dry solvent unless otherwise indicated. The metal complexes are optionally treated under light exclusion or yellow light. Solvents and reagents can be purchased from, for example, Sigma-ALDRICH or ABCR. The numbers quoted for each numerical value in the square brackets or for individual compounds are related to the number of CAS of known compounds from the literature.

General Manufacturing Method:

Reaction of monoaldehyde with monoamine and monoolefin

To a well stirred mixture of 500 mmol of arylamine, 550 mmol of aryl aldehyde, 1 mol of activated olefin and 1300 mL of dichloromethane, 100 mmol of Lewis acid are added and the mixture is then heated under reflux for 40 h. After cooling, the reaction mixture is washed twice with 400 mL water each time, the organic phase is dried over magnesium sulfate and the dichloromethane is removed under reduced pressure. The residue is dissolved in 1000 mL of o-dichlorobenzene, 5 mol of manganese dioxide is added, and the mixture is heated under reflux in a water separator for 16 h. After cooling, 1000 mL of ethyl acetate is added, the manganese dioxide is filtered under suction through a layer of celite, the manganese dioxide is washed with 1000 mL of ethyl acetate, and the combined filtrate is solvent removed under reduced pressure. The residue is recrystallized and finally the lower boiling water and non-volatile secondary components are removed by fractional sublimation (p about 10 ^-4 -10 ^-6 mbar, T about 150-400 ° C). The compound having a molar mass of greater than about 1200 g / mol is preferably removed by heat treatment under high vacuum to remove the solvent residue.

When a polyfunctional starter is used, the stoichiometry is adjusted accordingly.

Example A1

7,8,9,10-Tetrahydro-7,10-methano-6-phenylphenanthridine

A mixture of 46.6 g (500 mmol) of aniline [62-63-3], 58.4 g (550 mmol) of benzaldehyde [100-52-7], 94.2 g (1 mol) of norbornene [498-66-8] To a well stirred mixture of 1300 mL of dichloromethane is added dropwise 14.2 g (100 mmol) of boron trifluoride etherate [60-29-7], then the mixture is heated under reflux for 40 h. After cooling, the reaction mixture is washed twice with 400 mL of water each time, the organic phase is dried over magnesium sulfate, and then the dichloromethane is removed under reduced pressure. The residue is dissolved in 1000 mL of o-dichlorobenzene, 435 g (5 mol) of manganese dioxide is added and the mixture is heated under reflux in a water separator for 16 h. After cooling, 1000 mL of ethyl acetate is added, the manganese dioxide is filtered under suction through a layer of celite, the manganese dioxide is washed with 1000 mL of ethyl acetate, and the combined filtrate is solvent removed under reduced pressure. The residue is recrystallized twice from cyclohexane and finally the lower boiling and non-volatile secondary components are removed by fractional sublimation (p about 10 ^-4 -10 ^-5 mbar, T about 230 ° C). Yield: 76.0 g (280 mmol), 56%; Purity: ca. 99.5% by ¹ H NMR.

In a similar manner, the following compounds may be prepared:

Compounds of type A33 and then B, D, D, E, F and G can preferably be used as e-TMM, HBM, ETM, SMB and SEB.

Example A53

Functionalization of Substances by Suzuki Coupling

A solution of 22.5 g (50 mmol) of A49, 12.9 g (75 mmol) 1-naphthylboronic acid, 31.8 g (150 mmol) trisodium phosphate, 224.5 mg (1 mmol) palladium (II) 6 mmol) of tri-o-tolylphosphine, 200 mL of toluene, 50 mL of dioxane and 250 mL of water is heated under reflux with good stirring for 20 h. After cooling, the aqueous phase is removed, washed twice with 100 mL of water and 100 mL of saturated sodium chloride solution each time, and then filtered through a layer of celite to remove the palladium. After concentration, the residue is recrystallized five times from DMF and then fractionally sublimed twice under high vacuum (p ~ 10 ^-5 mbar, T: 280-300 0 C). Yield: 11.2 g (22.5 mmol), 45% of theory. Purity: 99.9% by HPLC.

In a similar manner, the following compounds may be prepared:

Example A57

Functionalization of materials by Buchwald coupling

22.5 g (50 mmol) of A49 and 22.6 g (60 mmol) of N- [1,1'-biphenyl] -4-yl-9,9-dimethyl-9H- fluorene [897671-69-1] A mixture of 7.2 g (75 mmol) sodium tert-butoxide, 224.5 mg (1 mmol) palladium (II) acetate, 263 mg (1.3 mmol) tri- tert- butylphosphine and 300 mL toluene was stirred at 20 h Lt; / RTI > under reflux with good stirring. After cooling, the reaction mixture is washed twice with 100 mL of water and once with 100 mL of saturated sodium chloride solution each time, and then filtered through a layer of celite to remove the palladium. After concentration, the residue is recrystallized 5 times from DMF and then fractionally sublimed (p ~ 10 ^-5 mbar, T: 300-310 ° C) under high vacuum. Yield: 14.3 g (19.5 mmol), 39% of theory. Purity: 99.9% by HPLC.

In a similar manner, the following compounds may be prepared:

The compounds A1-A27 can preferably be used as a two-terminal chelating ligand for transition metals, such as iridium and platinum, and as an electron-conducting triple matrix material (eTMM) or an electron transport material (ETM).

The compounds of type A28 ff., B, D, D, E, F and G are preferably selected from the group consisting of an electron-conducting triple matrix material (e-TMM), a hole blocking material (HBM), an electron transport material Can be used as anti-matter (SMB) and blue mono-emitter (SEB).

Example

Manufacture of OLED

1) Vacuum - Processing element:

OLEDs according to the present invention and OLEDs according to the prior art are produced by the general method according to WO 2004/058911, which is adapted to the situation described herein (changes in layer thickness, materials used).

In the following examples, results for various OLEDs are shown. Glass plaques with structured ITO (50 nm, indium tin oxide) form the substrate to which the OLED is applied. OLEDs have basically the following layer structure: Hole Transport Layer 1 (HTL1) (commercially available from Novaled) consisting of HTM doped with substrate / 3% NDP-9, 20 nm / hole transport layer 2 (HTL2) (EBL) / emission layer (EML) / optical hole blocking layer (HBL) / electron transport layer (ETL) / optical electron injection layer (EIL) and finally cathode. The cathode is formed by an aluminum layer having a thickness of 100 nm.

First, a vacuum-treated OLED is described. For this purpose, all materials are applied by thermal deposition in a vacuum chamber. In this case, the emissive layer always consists of one or more matrix material (host material) and a radioactive dopant (emitter), which is added to the matrix material (s) in a specific volume ratio by co-evaporation. The details given in this form as M3: M2: Ir (L1) ₃ (55%: 35%: 10%) are shown here in that the material M3 is present in the layer in a ratio by volume of 55% And Ir (L1) ₃ are present in a ratio of 10%. Similarly, the electron transporting layer may also consist of a mixture of two materials. The exact structure of the OLED can be found in Table 1. The materials used in the fabrication of OLEDs are shown in Table 4.

OLEDs feature a standard way. For this purpose, the electroluminescence spectrum, the power efficiency (measured in cd / A) and the voltage (measured in 1000 cd / m ² at V) are measured from the current-voltage-luminance characteristic (IUL characteristic). For selected experiments, the lifetime is measured. The lifetime is defined as the time after which the luminance falls from a certain starting luminance at a certain rate. LD50 value is the time specified in the life of the luminance, that is, for example dropped to 500 cd / m ² from 1000 cd / m ² is dropped to 50% of the starting luminance. According to the emission color, different starting emission is used. The value for lifetime can be converted to a value relating to other starting luminance with the help of a switching equation known to the person skilled in the art. In this context, the lifetime for a starting luminance of 1000 cd / m ² is a standard value.

Use of the compounds of the invention in OLEDs

The use of the compounds of the present invention includes applications as HTM, TMM, ETM, HBM, SMB and SEB in OLED.

Table 1: Structure of OLED

Table 2: Results for Vacuum-Treated OLEDs

2) Solution-processing element:

A: soluble functional material

The iridium complexes of the present invention can also be treated from solution, where they result in OLEDs having much simpler but nevertheless good properties with respect to process technology compared to vacuum-processed OLEDs. The preparation of these components is based on the production of polymeric light emitting diodes (PLED), which has been described several times in the literature (e.g. WO 2004/037887). The structure consists of a substrate / ITO / PEDOT (80 nm) / interlayer (80 nm) / emissive layer (80 nm) / cathode. For this purpose, a substrate (soda lime glass) from Technoprint is used, and an ITO structure (indium tin oxide, transparent conductive anode) is applied thereto. The substrate is cleaned in a clean room with DI water and detergent (Deconex 15 PF) and then activated by UV / ozone plasma treatment. Then, likewise in a clean room, as a buffer layer, an 80 nm layer of PEDOT (PEDOT is a polythiophene derivative from HC Starck, Goslar (Baytron P VAI 4083 sp.), Supplied as an aqueous dispersion) Lt; / RTI > The required spin rate is variable to the dilution and the specific spin-coat geometry (typical value for 80 nm: 4500 rpm). To remove the residue from the layer, the substrate is baked on a hot plate at < RTI ID = 0.0 > 180 C < / RTI > The used interlayer serves as a hole injection; In this case, HIL-012 from Merck is used. The interstices may alternatively also be replaced by one or more layers that must meet conditions that are not leached again by subsequent processing steps of EML deposition from solution. For the preparation of the emissive layer, the emitters of the present invention are dissolved together with the matrix material in toluene. A typical solids content of the solution is from 16 to 25 g / L when the layer thickness of 80 nm, which is typical of the device, is achieved by spin-coating, as here. The solution-treatment element contains a spinning layer consisting of (polystyrene): matrix 1: matrix 2: Ir _- G-Sol (25%: 25%: 40%: 10%). The spinning layer is rotated in an inert gas atmosphere, argon for the present invention, and baked at 130 캜 for 30 minutes. Finally, a cathode consisting of barium (5 nm) and then aluminum (100 nm) (high purity metal from Aldrich, especially barium 99.99% (Catalyst number 474711); deposition system from Lesker et al., Typical deposition pressure 5 x 10 ^-6 mbar) is applied by deposition. Optionally, it is possible to apply the hole blocking layer first and then apply the electron transporting layer and then only the cathode (e.g. Al or LiF / Al) by evaporation under reduced pressure. To protect the device from air and air humidity, the device is finally sealed and then characterized. The OLED example mentioned is more optimized; Table 3 summarizes the data obtained.

Table 3: Results from materials treated from solution

Table 4: Structure of the used materials

Claims (28)

A compound comprising at least one structure of the following formula (I) and / or (II):

Wherein the symbols used are as follows:
X is in each case the same or different and is CR or N;
E is a divalent bridge wherein the E group is taken together with the carbon atom to which it is attached to form a 5- or 6-membered ring;
Y is O, S, C (R) 2, C (R) = C (R), N (R), B (R), Si (R) 2, C = O, C = NR, C = C ( (R) ₂ , S = O, SO ₂ , C (R) ₂ -C (R) ₂ , P (R) and P (= O) R;
R is the same or different at each occurrence and, H, D, F, Cl , Br, I, N (R 1) 2, CN, NO 2, OH, COOH, C (= O) N (R 1) 2, _{^{Si (R 1) 3, B}} (OR 1) 2, C (= O) R 1, P (= O) (R 1) 2, S (= O) R 1, S (= O) 2 R 1, OSO ₂ R ¹ , a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms each of which may be substituted by one or more radicals R ^1, and one or more non-adjacent CH ₂ groups, where ^{R 1 C = CR 1, C≡C} , Si (R 1) 2, C = O, NR 1, O, S Or CONR ¹ and one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN), or have 5 to 60 aromatic ring atoms and in each case one or more R ¹ radicals Or an aromatic or heteroaromatic ring system which may be substituted by 5 to 40 aromatic ring atoms An aryloxy or heteroaryloxy group which may be substituted by one or more R < ¹ > radicals, or an aralkyl or heteroaralkyl group which may have 5 to 40 aromatic ring atoms and may be substituted by one or more R < ^{1 &} 10 to 40 which has an aromatic ring atom may be substituted by one or more radicals R ¹ diarylamino group, a di-heteroaryl-amino group, or an aryl-amino-heteroaryl group; At the same time, two adjacent R radicals may together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;
R ¹ is the same or different at each occurrence, is H, D, F, Cl, Br, I, N (R 2) 2, CN, NO 2, Si (R 2) 3, B (OR 2) 2, C (= O) R ² , P (═O) (R ² ) ₂ , S (═O) R ² , S (═O) ₂ R ² , OSO ₂ R ² , straight chain alkyl of 1 to 20 carbon atoms, A thioalkoxy group, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which may be substituted by one or more R ² radicals wherein one or more non-adjacent CH ₂ groups are ^{R 2 C = CR 2, C≡C} , Si (R 2) 2, C = O, NR 2, O, may be replaced by S or CONR ^2, in which one or more hydrogen An atom may be replaced by D, F, Cl, Br, I, CN or NO ₂ ), or an aromatic or heteroaromatic ring having 5 to 60 aromatic ring atoms and in each case optionally substituted by one or more R ² radicals Aromatic ring system, or having 5 to 40 aromatic ring atoms One or more R ² radicals in the aryloxy or heteroaryl which may be substituted by oxy group, or a 5 to 40 aromatic ring atoms to have aralkyl or heteroaralkyl optionally substituted with one or more R ² radical group, or a 10 A diarylamino group, a diheteroarylamino group or an arylheteroarylamino group which may have at least 40 aromatic ring atoms and may be substituted by at least one R ² radical; At the same time, two or more adjacent R < ¹ > radicals together or together with R < ¹ > may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;
R ² is in each case the same or different and is H, D, F or an aliphatic, aromatic and / or heteroaromatic hydrocarbyl radical of 1 to 20 carbon atoms in which one or more hydrogen atoms may also be replaced by F, ; At the same time, two or more R < ² > substituents may together form a mono- or polycyclic aliphatic ring system. The compound according to claim 1, wherein E is selected from the group of the formula X = XX = X, XWX, WX = X, X = XW
W is O, S, C (R) 2, N (R), B (R), Si (R) 2, C = O, S = O, SO 2, P (R) , and P (= O) R (Wherein R is in each case the same or different and is as defined in claim 1);
Wherein X is in each case the same or different and is as defined in claim 1. 3. A compound according to claim 1 or 2, characterized in that it comprises a structure of the formula (Ia) and / or (IIa)

Wherein the symbols used have the definitions given in claim 1. 4. A compound according to any one of claims 1 to 3, characterized in that it comprises a structure of the formula (Ia1), (Ia2), (IIa1) and / or (IIa2)

Wherein the symbols used have the definitions given in claim 1. 5. A compound according to any one of claims 1 to 4, characterized in that it comprises a structure of the formula (Ia3) and / or (Ia4)

Wherein the symbols used have the definitions given in claim 1. 3. A compound according to claim 1 or 2, characterized in that it comprises a structure of the formula (Ib) and / or (IIb)

Wherein the symbols used have the definitions given in paragraphs 1 or 2. 3. A compound according to claim 1 or 2, comprising a structure of formula (Ic): < EMI ID =

Wherein the symbols used have the definitions given in claim 1, and E in each case may be the same or different. 8. A compound according to any one of claims 1 to 7, having two or more bicyclic groups formed by structural elements comprising a group Y, wherein Y may in each case be the same or different and is selected from the group consisting of ≪ / RTI > 9. A compound according to any one of claims 1 to 8, characterized in that it comprises the structure of the formula CyE- (CyF) _n wherein the symbols and indices are:
n is 2 or 3,
CyE is a structural element selected from the following formulas:

CyF is one or more structural elements selected from the following formulas:

Wherein the symbols E, R, Y and X used have the definitions given in claim 1 and U is O, S, C (R) ₂ , N (R), B (R) ₂ , C = O, S = O, SO ₂ , P (R) and P To CyE at the position indicated by #. 10. A compound according to claim 9 wherein CyF is at least one structural element selected from the following formulas:

Wherein the symbols R, Y and X used have the definitions given in claim 1, the dashed lines of the formulas CyF-3 and CyF-4 represent a bond to CyE, and CyF represents the position indicated by # in each case To CyE]. 11. Compounds according to any one of claims 1 to 10, having the structure of the formula CyG (CyH) _n , wherein CyG and CyH in each case together form a ring and the symbols and indices are as follows: :
n is 2 or 3,
CyG is a structural element selected from the following formulas:

CyH is one or more structural elements selected from the following formulas:

In the formula, have the symbols R, Y and X are defined as given in claim 1, wherein using, U is O, S, C (R) 2, N (R), B (R), Si (R) 2, C = o, S = o, SO 2, is selected from P (R), and P (= o) R, formula the dotted line in CyH-1 and CyH-2 represents the bond to the CyG, CyH is at each occurrence o To form a ring by bonding to CyG at a position represented by " R " 12. Compounds according to any one of claims 1 to 11, characterized in that compounds of the formula are excluded:

. 13. The compound according to any one of claims 1 to 12, having a content of bromine atoms of 18% by weight or less. 14. A compound according to any one of claims 1 to 13, characterized in that it is in the form of an enantiomeric mixture, preferably a mixture of diastereoisomers. (Ia3), (Ia2), (IIa2), (Ia3), (Ia2), (Ia3) , (Ia4), (Ib) , (IIb) and (Ic) and formula CyE- structure (CyF) _n and CyG (CyH) in the structure of the _n symbol X is the ratio of CR to N is selected to be three abnormalities of ≪ / RTI > 16. The compound according to any one of claims 1 to 15, having a glass transition temperature of at least 110 < 0 > C. 17. The compound according to any one of claims 1 to 16, having a molecular weight of up to 5000 g / mol. 18. The compound according to any one of claims 1 to 17, comprising at least one metal atom selected from iridium and platinum. An oligomer, polymer or dendrimer comprising one or more compounds according to any one of claims 1 to 18 wherein at least one bond of the compound to the polymer, oligomer or dendrimer is present. A composition comprising at least one compound according to any of claims 1 to 18 and / or an oligomer, polymer or dendrimer according to claim 19 and a fluorescent radiator, a phosphorescent emitter, a host material, a matrix material, an electron transport material, Wherein the composition comprises at least one further organic functional material selected from the group consisting of a hole conductor material, a hole injecting material, an electron blocking material and a hole blocking material. 18. A formulation comprising one or more compounds according to any one of claims 1 to 18, oligomers, polymers or dendrimers according to claim 19 and / or one or more compositions according to claim 20 and one or more solvents. A process for preparing a compound according to any one of claims 1 to 18 or an oligomer, polymer or dendrimer according to claim 19 by reacting at least one aldehyde with at least one aromatic or heteroaromatic amine and at least one bicyclic olefin . 23. The process of claim 22, wherein the intermediate obtained after the reaction of at least one aldehyde with at least one aromatic amine and at least one bicyclic olefin is converted in the coupling reaction. A compound according to any one of claims 1 to 18 or an oligomer according to claim 19 in an electronic device as a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron blocking material and / , Polymer or dendrimer, or at least one of the compositions according to claim 20. An electronic device comprising at least one compound according to any one of claims 1 to 18 or an oligomer, polymer or dendrimer according to claim 19 and / or at least one composition according to claim 20, A preferable organic electroluminescent device is an OLED and an OLEC, and a very particularly preferable organic electroluminescent device is an organic electroluminescent device. Examples of the organic electroluminescent device include organic laser diodes, organic light emitting transistors, organic light emitting diodes (OLED) An electroluminescent device is an OLED), an organic integrated circuit, an organic field-effect transistor, an organic thin film transistor, an organic solar cell, an organic optical detector, an organic photoreceptor and an organic field-quench device. The organic electroluminescent device according to claim 25, wherein the organic electroluminescent device is preferably an OLED or OLEC, and more preferably an OLED, wherein the compound according to any one of claims 1 to 18 or the oligomer, polymer or Wherein the dendrimer or the composition according to claim 20 is used as radioactive compound and / or matrix material in at least one radiation layer, preferably in combination with additional matrix material and / or additional radioactive compound. 26. The organic electroluminescent device according to claim 25 or 26, wherein the compound according to any one of claims 1 to 18 and / or the oligomer, polymer or dendrimer according to claim 19 and / Wherein the composition according to claim 1 is used as an electron-conducting compound in at least one electron-conducting layer. 28. The organic electroluminescent device according to any one of claims 25 to 27, wherein the compound according to any one of claims 1 to 18 and / or the oligomer, polymer or dendrimer according to claim 19 and / Or the composition according to claim 20 is used as a hole-conducting compound in at least one hole-conducting layer.